DE2341895B2 - POLYMER BLENDS BASED ON POLYAMIDES, PHOSPHORUS COMPOUNDS AND ALKALIMETAL COMPOUNDS WITH REDUCED GEL FORMATION - Google Patents

Description

R ₅ OP-OR ₇

and

15th

B) at least one alkali metal compound Shape!

Z-OR ₈

20th

are incorporated into the polyamide, the amount of component (A) 50 to 1000 ppm (calculated as phosphorus), based on the weight of the polyamide, and the amount of component (B) I to 5 mol (calculated as alkali metal) per mole of component (A), and in the formulas Ri to R7 are hydrogen, alkyl, aryl or cycloalkyl, R _{8 is} hydrogen, alkyl, aryl or cycloalkyl, Xi to X _{5 are} each hydrogen, alkyl, aryl, cycloalkyl or alkali metal stand, Z is an alkali metal and one of the radicals R _r to R ₇ and one of the radicals Xi to X? together form a ring.

The invention relates to mixtures based on polyamides, phosphorus compounds and alkali metal compounds with significantly reduced gel formation in the molten state, especially mixtures Based on polyamides of the diamine-dicarboxylic acid type with prevented gel formation through thermal degradation.

Polyamides, especially of the diamine-dicarboxylic acid type, e.g. B. polyhexamethylene adipamide and polyxylylene adipamide, have poor thermal stability when molten. If they are kept at high temperature for a long time, they go even in an oxygen-free system into a non-meltable substance with a three-dimensional network structure above. The presence of such a substance in a normal polymer is even the slightest Quantity is known to have detrimental effects on the smooth operation of large-scale production, e.g. B. Polymerization, spinning, drawing and shaping. The effective prevention of this gelation of molten polyamides is therefore very desirable, and numerous attempts to solve the problem have already been done. Be: Many of these attempts are only methods for Prevention of thermal oxidation of polyamides at temperatures below their melting point in an oxygen-containing system. The prevention of gel formation in polyamides due to thermal degradation thus is useful at temperatures above their melting point in an oxygen-free system not possible.

It was also proposed that the gelation of polyamides by thermal degradation in the molten Condition in an oxygen-free system by adding certain additives, e.g. B. of pyrophosphites, organic phosphinic acid amides, magnesium salts of mono- or diesters of phosphorous acid, of Barium salts of mono- or diesters of phosphorous acid or orthophosphoric acid, of copper salts of mono- or diesters of orthophosphoric acid and the like. To prevent (Japanese patents 11836/70, 35 667/70, 12 986/70, 38 351/70, 38 352/70 etc.). However, the incorporation of these additives sometimes has undesirable consequences, e.g. B. an increase in Viscosity of the polymer, excessive foaming and insufficient miscibility of the polymer with the Additives. In addition, it is not essential on the effect of preventing gelation Determine the difference compared to the non-use of additives. Even if one If there is a difference, the gelation time is only extended 1.2 to 1.5 times, so that one sufficient and effective prevention of gel formation is not to be expected.

Furthermore, the admixture of phosphorus compounds and alkali halides to polyamides. The admixture of these additives improves only the thermal stability with strong elongation of molded parts made of the polyamides, z. B. fibers, however no effect of preventing gelation of the molten polyamide can be obtained.

GB-PS 12 27 146 relates to the production of a polyamide foam, an oxyacid being phosphorus and a metal carbonate is introduced into the polyamide and the resulting mixture is heated. Since the Reaction between the oxyacid of phosphorus and the metal carbonate for the purpose of foaming only in the form because of the desired .Ziel is to take place, the simultaneous presence of the two components must can be avoided in the polymerization.

The present invention has the object of avoiding gel formation in a polyamide that is in molten state. Furthermore, a phosphorus compound and an alkali metal compound must be used be present in the polyamide when it is heated. They can also be added during the polymerization.

According to GB-PS 12 27 146 the suitable oxyacids of phosphorus include all acidic oxyphosphorus compounds such as B. (a) hypophosphorous acid, (b) alkylphosphonic acids and dialkylphosphonic acids, (c) phosphorous acid, (d) alkylphosphonic acids and their monoesters, (e) orthophosphoric acid and their Partial esters, (f) metaphosphoric acid, (g) pyrophosphoric acid and (h) hexametaphosphoric acid and trimetaphosphoric acid.

In contrast, according to the present invention, only reductive oxyphosphoric acid compounds can be used use. None of the above compounds (e), (f), (g) and (h) are effective.

According to GB-PS 12 27 146 the metal carbonate can be any which is decomposable by an acid and the metal component can be one of the following (a) metals of groups IA and HA of the periodic table, (b) rare earth metals; and (c) gallium, indium, tallium, lead, manganese, iron, cobalt and nickel.

In contrast, according to the present invention, only the compounds of metals from group IA des Periodic table can be used. The compounds of the metals of group HA, the rare earth metals and the

Metals mentioned under (c) are not effective, but even cause gel formation and decomposition of the polyamide. In addition, hydroxides and alkoxides are useful in the present invention.

According to GB-PS 12 27 146 (p. 2, left column, lines 17 to 20) the oxyacids of phosphorus in amounts of 0.5 to 10 mol% and the metal carbonates in Amounts of 0.5 to 50 mol% are used per monomer unit of polyamide. That is, relatively large Quantities of these additives are used.

In contrast, according to the present application, the phosphorus compound is used in an amount of 50-1000 ppm, which is 0.0425-0.85 mole percent, is used when the polymer is nylon 66. Furthermore, the amount of the alkali metal compound (B) is 1 to 5 equivalents. From this it can be seen that these amounts are relatively small compared to the amounts used in GB-PS 1227 146.

From the comparison shown above, it can be clearly seen that the present invention from GB-PS 12 27 146 regarding the target selfling and the Solution is completely different.

JA-AS 69 02 583 describes the production of aromatic polyamides in a stable state, whereby the aromatic polyamide compositions are convertible into a heat resistant polymer having a benzoxazinone ring contains in the main chain. As from the partial English translation of JA-AS 69 02 583 shows, this concerns the stabilization of a solution of a polyamide in an organic solvent, to prevent gel formation in the solution and not stabilize the polyamide itself in molten state.

In JA-AS 69 02 583 it is described that the aromatic polyamide, which is preferably treated is an aromatic polyamide that contains water and is in a swollen state, which is caused by Introduction of water into the polymer mixture is obtained by using polymerization of polyphosphoric acid as a polymerization medium. Another revelation or Description regarding the use of any phosphorus compound is not given. In addition, as can be seen from the description (English translation) of Example 1, by polymerization Polymeric mixture obtained in polyphosphoric acid with large amounts of water and aqueous Na2CO3 solution washed in the course of recovering the polyamide from the polymer mixture. It follows that the aromatic polyamide treated according to JA-AS does not contain any phosphorus compounds.

It will then be seen that the object and purpose of the JA-AS is defined by the present invention are completely different.

The object of the invention is to provide mixtures based on polyamides, phosphorus compounds and alkali metal compounds, particularly diamine-dicarboxylic acid type polyamides, with strong reduced tendency to gel.

The invention also addresses the problem of the poor thermal stability of molten Polyamides of the diamine-dicarboxylic acid type, in this state, even in an oxygen-free system easily form gels, improve them and thereby prevent gel formation. The invention includes In addition, additives intended for incorporation into polyamides, especially those of the diamine-dicarboxylic acid type, the gel formation time of the polymer in the molten state compared to conventional additives extend considerably, are readily miscible with the polymer and do not lead to an increase in viscosity or lead to foam formation.

The invention relates to mixtures based on polyamides, phosphorus compounds and alkali metal compounds with reduced tendency to gel, containing a polyamide and

A) at least one of the following phosphorus compounds:

a) Phosphinic acid compounds of the formula
O

R ₁ -P-OX ₁

b) Phosphonous acid compounds of the formula

OX ₂

R ₃ -P-OX ₃

c) phosphonic acid compounds of the formula

Il

R ₄ -P-OX ₄

ox _s

d) Phosphorous acid compounds of the formula
OR ₆

R ₅ OP-OR ₇

B) at least one alkali metal compound of the formula

Z-OR ₈

possibly together with

C) at least one cyclic dicarboxylic acid anhydride of the formula

/ \
O = CC = O

and / or its hydrolyzed product and / or

D) at least one o-phenylenediamine and / or its derivative,

wherein the amount of component (A) 50 to 1000 ppm (calculated as phosphorus), based on the weight of the Polyamide, the amount of component (B) 1 to 5 moles (calculated as alkali metal) per mole of the component (A), the amount of component (C) 0.01 to 2% by weight based on the weight of the polyamide, and the amount aer component (D) 0.01 to 2 wt .-%, based on the Weight of the polyamide.

In the above formulas, R 1 to R 7 are each hydrogen, alkyl, aryl or cycloalkyl; R ₈ represents hydrogen, alkyl, aryl or cycloalkyl; Xi to X are ₅

each hydrogen, alkyl. Aryl, cycloalkyl or Alkali metal and z stone for an alkali metal. One of the radicals Ri to R7 and one of the radicals Xi to X 'can together form a ring. Y looks for a group of the formula

or

R R

in which the radicals R are identical or different and represent hydrogen. Alkyl, substituted alkyl. Aryl, cycloalkyl, halogen, nitro or hydroxyl, while R 'is an alkyl radical and η is an integer from 1 to 4.

The polyamides to which the invention is applicable. may be of the diamine dicarboxylic acid type. as specific examples are

Poly hexaniethyleneadipic acid amide,

Polyhexamethylene sebacic acid amide.

Polyxylylene adipic acid camide,

Polyxylylene sebacic acid camide,

Polyhexamethylene isophthalic acid amide,

Poly-p-xylylene dodecainide and

Polycyclohexanebismethylendodecamide

to call.

The copolymers and mixtures of these polyamides are also suitable.

It is generally believed that gelation in polyamides is caused by some mechanism in which the terminal amino groups of the molecule to form a secondary amine and Elimination of ammonia react with each other, and that from this bridging point of the amine the Spatial network structure is formed between the molecules. The presence of such secondary amines was confirmed by analysis of gelled polymers. The phosphorus compound (A) in the polyamide blends stabilize according to the invention! the terminal amino groups of the polymer and prevents their reaction to form a secondary amine. By simply adding the phosphorus compound (A) a certain inhibiting effect on gel formation can be achieved, but the Effect significantly increased in the presence of the alkali metal compound (B).

Suitable phosphorus compounds (A) are, for example, phosphinic acid compounds, e.g. B. dimethylphosphinic acid c. Phcnylmethylphosphinäure, compounds of the formula

O P O

Ii

O = P O

CH,

in and their hydrolysates and condensates,

Phosphonous acid compounds, / .. B.

Phenylphosphonous acid c. Sodium phenylphosphonite.
Potassium phenylphosphonite. Uthium phenyl

phosphonite.

Ethylphosphonite, lypophosphorous acid,

Sodium hypophosphite, potassium hypophosphite.

I. lithium hypophosphite and ethyl hypophosphite.
Phosphonic acid compounds, e.g. B.

Phcny Iphosphonic acid, ethyl phosphoric acid,

Sodium phenylphosphonate,

Uthiumphcnylphosphonat, Kaliumphcnylphosphonat,
Diethylphenylphosphonai, sodium ethyl

phosphonate and

Potassium ethyl phosphonate,

Compounds of phosphorous acid, / .. B.

phosphorous acid, monosodium hydrogenjo phosphite,

Disodium hydrogen phosphite, triethyl phosphite,

Triphenyl phosphite and

pyrophosphorous acid.

3-, It is generally advantageous to use Hypophosphorous acid, sodium hypophosphite, potassium hypophosphite or the like.

Suitable alkali metal compounds (B) are, for example, sodium hydroxide, sodium methoxide, sodium ethoxide, Sodium propoxide, sodium butoxide, potassium methoxide, lithium methoxide and sodium carbonate.

The amount of component (A) to be admixed with the polyamide is in the range from 50 to 1000 ppm, expediently in the range from 100 to 500 ppm, calculated as phosphorus and based on the polyamide. If the If the amount is less than 50 ppm, no sufficient gelation inhibiting effect can be obtained. if the amount is greater than 1000 ppm, becomes the inhibitory Effect on gel formation is not further increased, so that the use of such a large amount of Phosphorus compound is uneconomical.

The component (B) is used in such an amount that the molar ratio of alkali metal the total to the phosphorus compound is 1 to 5, preferably 2 to 4. At a molar ratio of less than 1, the gelation of the polyamide is accelerated although the viscosity is increased. At a molar ratio if more than 5, the viscosity becomes insufficient and the formation is particularly deteriorated Pressure accelerates. In addition, the use of such a large amount of the compound is dated economic point of view unfavorable.

As mentioned earlier, can have an excellent inhibiting effect on gel formation through the combined use of the phosphorus compound and the alkali metal compound can be achieved. One such an effect can be achieved through the additional admixture of the chemical dicarboxylic acid anhydride or its

lysed product (C) and / or of o-phenyldimine or its derivative (D) can be amplified in certain amounts. The one brought about by component (C) Reinforcement effect is likely due to their selective reaction with the terminal amino groups pen and the resulting blocking of these amino groups, while the reinforcing Effect of the component (D) on the blocking of those reactive with the secondary amine Can be attributed to carboxyl groups. It is in it should also be noted that the addition of component (D) also reduces the fertility of the Polyamides is effectively improved.

Examples of suitable cyclic dicarboxylic anhydrides (C) or their hydrolyzed products are ι ■ ->

Phthalic anhydride. Phthalic acid.

Tetrahydrophthalic anhydride, 4-1 hydroxyphthalic anhydride.

j-Niirophthalic acid,

I ^ -Cyciohexanedicarboxylic anhydride, maleic anhydride, M el hy I maleic anhydride, 4-methyltetralihydro-o-phthalic acid, 4-chloromethyl tetrahydro-o-phthalic acid, J-methyl-tetrahydro-o-phthalic anhydride and the compound of the formula

CO

20th

Of these compounds, phthalic anhydride is particularly preferred.

Suitable o-phenylenediamine (D) and its derivatives are, for example

N-methyl-o-phenylenediamine,
3-methyl-o-phenylenediamine,
4-methyl-o-phenylcndiamine,
Ν, Ν'-Dimethyl-o-phenylenediamine and N-Phcnyl-o-phenylenediamine.

Compounds which are decomposed to these o-phenyl compounds at high temperature are also available suitable.

The amounts of components (C) and (D) used in the polyamide blends according to the invention are each 0.01 to 2 Ciow .-%, preferably 0.1 to 1% by weight, based on the weight of the polyamide. When the amount is less than 0.01% by weight, the gelation inhibiting effect is unsatisfactory. When it is more than 2% by weight, the spinning processability is deteriorated, and so does one Increase in the inhibiting effect on gel formation is no longer to be expected.

The polyamide blends according to the invention can contain other additives, e.g. B. matting agents, Viscosity stabilizers, light stabilizers and heat stabilizers, can be added.

The admixture of the above-mentioned essential and optionally added additives can before

h ^r > or take place during the polymerization to produce the polyamide. It is also possible to mix these additives with the polymer formed in the molten state or in the form of a solution. The addition can take place all at once or separately in different process stages.

The molecular weight of the polymers obtained is determined by the addition or by the addition time of these Additives hardly affected.

The polymerization for the production of the polyamides can be carried out in any suitable manner in a customary manner Polymerization apparatus, e.g. B. continuously operating pressure polymerization reactors, continuously carried out at normal pressure Poiymerisationsreaktor or in polymerization autoclaves will.

Embodiment c and currently preferred embodiments of the invention are described in the following examples. In these examples means the solution viscosity the relative viscosity, represented by the ratio of the value of the viscosity of a Solution of the polymer (1 g) in 96% sulfuric acid (100 ml), determined at 25 ° C using a Ostwald viscometer, to the value of the viscosity of 96% sulfuric acid alone, determined in the same Way. The gel formation time is the time in hours that is required to convert the polymer to 98% strength lOO'Vuiger to make formic acid insoluble when pouring it to a certain temperature Steam of a certain pressure is heated. The insolubility of the polymer in formic acid is confirmed by the following method:

The polymer is ground to a particle size of 0.84 to 2 mm. The powder (0.1 g) is in a Flask into which 98% to 100% formic acid (20 ml) is added. The flask is 4 hours allowed to stand, whereupon the state of the polymer is observed. If the polymer is not a gel contains, it is completely dissolved in the solvent in 4 hours. If, on the other hand, the polymer is a Gel contains, the particles are only moistened and swollen by the solvent during a uniform formic acid solution is not obtained after 4 hours. Moistened by the presence of this and swollen polymer, the gelation of the polymer is confirmed.

example 1

In an autoclave 500 g of the salt of m-xylylcndiamine with adipic acid, 1000 g of distilled Added water and the additives mentioned in Table I, whereupon the air is displaced by nitrogen will. The temperature is raised while water is distilled off so that the internal pressure is kept at 10 kg / will. When an internal temperature of 260 "C is reached, the internal pressure gradually becomes inside reduced from 90 minutes to normal pressure, whereupon reaction do another hour with animal like Temperature and at the same pressure. The polymer formed is with nitrogen, the Supplied from outside the reaction system is pressed out, passed through a cooling bath and shredded. The solution viscosity and the gel formation time at 27O "C under a flowing water vapor of normal pressure for the in this way produced polymer measured. The results are given in Table 1.

Tabel

No additives

Phosphorus compound

Quantity *) alkali metal compound

Lot**)

Solution viscosity

Gel formation line, std.

1 not added - not added - 2.23 18th 2 Phenylphosphonic acid 200 not added - 2.25 16 3 Sodium phenylphosphonite 200 not added 1 2.25 24 4th Sodium phenylphosphonite 200 Sodium hydroxide 2 2.23 33 5 Sodium phenylphosphonite 200 Sodium hydroxide 4th 2.20 38 6th Sodium phenylphosphonite 500 Sodium hydroxide 2 2.25 40 7th Ethyl phenyl phosphonite 200 Sodium hydroxide 2 2.22 33 8th Sodium hypophosphite 200 not added 1 2.23 20th 9 Sodium hypophosphite 200 Sodium methoxide 2 2.27 35 10 Sodium hypophosphite 200 Sodium methoxide 3 2.23 41 Il Potassium hypophosphite 200 Potassium methoxide 5 2.17 45 12th Diethylphosphinic acid 200 Sodium hydroxide 2 2.23 34

*) Parts by weight per million (ppm), calculated as phosphorus and based on the polyamide. **) Molar ratio of total alkali metal to phosphorus compound.

The results in the table show that by adding the phosphorus compound and the alkali metal compound excellent results can be obtained.

Example 2

The polymerization is carried out in the manner described in Example I with 500 g of the salt of hexamethylenediamine with adipic acid, 500 g of distilled water and the additives listed in Table 2, but the internal temperature is increased to 275 ° C. The solution viscosity and the gel formation time at 290 " ⁵ C under flowing steam and at normal pressure are measured for the polymer formed. The results are given in Table 2.

Table 2

No additives

Phosphorus compound

lot

Alkali metal compound

lot

Solution vision

Cielhil-

dungs / express,

Hours.

1 not added

2 sodium hypophosphite

3 sodium hypophosphite

not added 200 not added 200 sodium hydroxide

2.70
2.72
2.72

27
30th
50

For the quantities given, the subnotes / u apply Table 1 in Example I.

The values in the table show that there is a remarkable synergistic effect on the extension the (ielbiklungs / eit by adding a phosphorus compound and the alkali metal compound can be reached.

Example i

Poly-m-xylylene adipic aniide is prepared in the manner described in Example I, but using a nylon sal / es. which contains 1.0 mol% of excess adipic acid as a viscosity stabilizer, and produced without / us;)! / ties gel formation inhibitor. The polymer formed is mixed mil ilen in Table I referred to / iisätzen in a molten state, cooled, and crushed. The solution viscosity and the Cielhildungs / cit of the resulting polymer are measured. The results are given in Table J.

Table 3

No additives

Phosphorus compound

lot

Alkali metal prevention

lot

Solution viscosity Hours.

1 not added

2 sodium phenylphosphon.it

3 sodium phenylphosphonite

4 sodium phenylphosphonite

5 not added

6 not added

*) The amount corresponding to the molar ratio Na / P = 2, provided that 200 ppm of phosphorus are added.

- not added - 2.00 25th 200 not added 1 2.02 27 200 Sodium aloxide 2 2.00 44 200 Sodium ethoxide 10 1.33 50 - Sodium hydroxide 1.29 *) ■ 10 ^s 1.92 28 (Mol / g) - Sodium acetate 1.29 *) ■ 10 " ⁵ 1.86 30th (Mol / g)

The footnotes in Table 1 apply to the quantities.

The values in the table show that when the gelling inhibitor is added after the polymerization, almost the the same results were obtained as when the gel formation inhibitor was added before the polymerization (Example 1) will. It can also be seen that the solution viscosity of the polymer is reduced by the addition of sodium acetate decreased and thereby the gel formation time can be extended to a certain extent, but that the Effect is less than that of the combination of the phosphorus compound and the alkali metal compound.

30th

Example 4

The polymerization is carried out in the manner described in Example I using 500 g of the salt of ni-xylylenediamine with adipic acid, 1000 g of distilled water and the additives listed in Table 4. The solution viscosity and the gel formation cell at 270 ^° C. under flowing steam at normal pressure are measured for the polymers formed. The results are given in Table 4.

Table 4

No additives

Phosphorus compound

Amount of alkali metal compound

lot

Solution viscosity

üelbil-

duiigszcit,

Hours.

1 not added

2 phenylphosphonic acid

3 sodium phenylphosphonate

4 sodium phenylphosphonate

5 sodium phenylphosphonate

6 sodium phenylphosphonate

7 sodium phenylphosphonate

8 sodium phenylphosphonate

9 sodium phenylphosphonate

10 monosodium hydrogen phosphite

11 monosodium hydrogen phosphite

not added - 2.24 17th 200 not added - 2.26 16 200 not added 1 2.25 21 200 Sodium hydroxide 3 2.24 34 200 Sodium hydroxide 5 2.19 38 200 Sodium hydroxide 10 1.30 32 30th Sodium hydroxide 3 2.23 20th 500 Sodium hydroxide 3 2.18 42 1000 Sodium hydroxide 3 2.08 45 200 Sodium hydroxide 3 2.23 34 200 Sodium hydroxide 5 2.19 40

The footnotes of apply to the quantities Table 1.

The results show that by adding the phosphorus compound together with the alkali metal compound a remarkable effect can be achieved.

Example 5

The polymerization is carried out in the manner described in Example I using 500 g of the Salt of hexamethylenediamine with adipic acid, 500 g of distilled water and those mentioned in Table 5 Additives carried out, however, the internal temperature is increased to 275 ° C. The solution viscosity and gel formation time at 290 ° C under flowing Water vapor at normal pressure is measured for the polymers formed. The results are mentioned in table 5.

Table 5

No. Additives lot Alkali metal lot Solution Yellowil Phosphorus compound v.:binding viscosity training time, _ not added - Hours. ι not added 200 not added 2 2.70 27 2 Monosodium hydrogen phosphite 200 Sodium hydroxide 3 2.70 29 3 Monosodium hydrogen phosphite - Sodium hydroxide 1.29 *) · 10 ~ 2.68 48 4th not added (Mol / g) ⁵ 2.55 31

*) The amount corresponding to the molar ratio Na / P = 2, provided that 200 ppm phosphorus are added.

The footnotes for thermal degradation are shorter for the quantities. The results of this

Table 1. Examples show that a remarkable synergistic

The gel formation time of the polymer has an effect on the prolongation of the gel formation time

increasing molecular weight or increasing solubility through the combined use of phosphorus

Solution viscosity under the same conditions of the bond and the Alkalinieiallverbindiing is achievable.

Example 6

Poly-m-xylylene adipamide is prepared in the manner described in Example 1 using a mixture of the salt of m-xylylenediamine with adipic acid and distilled water in the absence of additives. The polymer obtained is melted and with the properties shown in Table 6 30

kneaded additives mentioned. The product is cooled and crushed. The solution viscosity and the gel formation time at 270 ^° C. under flowing steam at normal pressure are measured for the polymers obtained. The results are given in Table 6.

Tabel 6th lot Alkali metal
link lot Solution
viscosity Yellowil
training time,
Hours. No. Additives
Phosphorus compound 200
200 not added
not added
Sodium ethoxide
Sodium acetate 1
3
1.29 *) · 10 ~ ⁵
(Mol / g) 2.24
2.25
2.23
2.02 17th
20th
36
22nd 1
2
3
4th not added
Sodium phenylphosphonate
Sodium phenylphosphonate
not added

*) Amount corresponding to the molar ratio Na / P = 2, provided that 200 ppm of phosphorus are added.

The footnotes in Table 1 apply to the quantities.

A comparison of the results with the results obtained according to Example 4 shows that by adding the Gelation inhibitor after the polymerization has almost the same effect as when the gelation inhibitor was added is achieved prior to polymerization. By adding sodium acetate, the solution viscosity of the Polymer low; and thereby the gelation time can be extended to some extent, however the effect is less than when the phosphorus compound is combined with the alkali metal compound.

Example 7

Poly-m-xylylene adipamide is applied to the in Example 1 prepared manner described, wherein as a gel formation inhibitor sodium phenylphosphonite in a Amount of 200 ppm, calculated as phosphorus and based on the polyamide, and sodium hydroxide in in an amount such that the molar ratio of total alkali metal to phosphorus is 2 amounts to. For comparison, a polymerization is carried out without adding the gel formation inhibitor. the the two polymers obtained have a solution viscosity of 2.25.

The polymers are spun into threads by melt spinning under the following conditions:

Spinning temperature 260 ⁰ C; Diameter of the nozzle 0.3 mm; Number of nozzle bores 20; Throughput 12.3 g / min .; Take-off speed 910 m / min. The product is then drawn at a draw ratio of 3.1 at a speed of 640 m / minute,

b5 where a light, good looking yarn of 40 d / 20 f is obtained. When the polymer, which does not contain a gel formation inhibitor, is spun, the yarn breaks often at the nozzle after continuous spinning for

709 583/254

about 2 days, during which the back pressure at the nozzle increases rapidly so that spinning becomes impossible. Against it the polymer containing the gel formation inhibitor is spun smooth and stretched. After continuous Spiders rarely kick for about 1 week

Table 7

Yarn breaks at the nozzle and an increase in de; Back pressure in the nozzle is not detected. The number the knot per million meters of drawn yarn; is determined by the slit method The results are shown in Table 7 below.

Spinning time, Number of knots per Million meters hours drawn yarn Gel inhibitor added not added 12th 4th 3 24 3 12th 36 7th 178 48 4th - 72 8th - 96 10 - 144 7th _

Example 8

The polymerization is carried out in the manner described in Example 1 using 500 g of the Salt of m-xylylenedianiine with adipic acid, 1000 g distilled water and the additives listed in Table 8. The product comes with Nitrogen introduced from outside the reaction system is pressed out by a cooling bath

Table 8

directed and shredded. The solution viscosity and the Gel formation time at 270 ° C under flowing steam of normal pressure are measured for the polymers produced. The results are shown in Table t called. They show that in comparison to other polymers with the same solution viscosity Gel formation in the polymers containing the phosphorus compound, the alkali metal compound and the component (C) is suppressed to a remarkable extent.

No. Additives Men
ge *) Phosphorus compound Men
ge **) alkali
metal Men
ge **) Polymeri Lö- GeI- Component (C) link station
conditions sensational
viscous bil-
manic not added _ not activity Time,
Hours. I. not added added Normal pressure 2.23 18th - phenylphos- 200 not - 2 not added phonic acid added Normal pressure 2.25 16 - phenylphos- 200 Sodium- 2 3 not added phonic acid hydroxide Normal pressure 2.23 38 - Sodium- 200 sodium 3 4th not added hypophosphite hydroxide Normal pressure 2.24 37 - Phenylphosphonic 200 sodium 2 5 not added acid hydroxide Normal pressure 2.23 38 - phosphorous acid 200 lithium 3 6th not added hydroxide Normal pressure 2.23 38 0.45 not clogged - not - 7th Phthalic anhydride added diminished 2.23 40 0.40 not added - not - pressure 8th Caproic acid added diminished 2.23 20th 0.28 not added - not - pressure 9 Adipic acid added diminished 2.23 11th 0.52 not added - not - pressure ■ 10 Tetrahydrophthalic added diminished 2.24 37 acid anhydride pressure

20th

continuation

No. Additives Men
ge *) Phosphorus compound Men
ge **) Alkali-
metal- Men
ge **) Polymeri Lö- Gel- Hours. Component (C) connection station
conditions education
viscosifying 37 0.38 not added _ not _ UiI - ™. " 11th 1,2-cyclohexane added diminished 2.23 90 dicarboxylic anhydride 0.45 phenylphos- 200 sodium 2 pressure 12th Phthalic anhydride phonic acid hydroxide diminished 2.23 43 0.40 phenylphos- 200 Sodium- 2 pressure 13th Caproic acid phonic acid hydroxide diminished 2.22 25th 0.28 phenylphos- 200 Sodium- 2 pressure 14th Adipic acid phonic acid hydroxide diminished 2.22 84 0.52 phenylphos- 200 Sodium- 2 pressure 15th Tetrahydrophthalic phonic acid hydroxide diminished 2.23 92 acid anhydride 0.51 phenylphos- 200 Sodium- 2 pressure 16 Phthalic acid phonic acid methoxide diminished 2.23 80 0.30 phenylphos- 200 Sodium- 2 pressure 17th Maleic anhydride phonic acid methoxide diminished 2.24 90 0.51 phenylphos- 200 lithium 2 pressure 18th Phthalic acid phonic acid hydroxide diminished 2.23 90 0.51 Sodium hydrogen 200 sodium 2 pressure 19th Phthalic acid phosphite hydroxide diminished 2.23 44 0.51 phosphorous acid 200 sodium 8th pressure 20th Phthalic acid hydroxide diminished 1.53 98 0.51 phosphoric acid 500 Sodium- 2 pressure 21 Phthalic acid hydroxide diminished 2.18 130 2.00 phosphoric acid 200 Sodium- 2 pressure 22nd Phthalic acid hydroxide diminished 1.45 110 0.51 Sodium di- 200 Sodium- 2 pressure 23 Phthalic acid methyl phosphinate hydroxide diminished 2.19 pressure

*) In% by weight, based on polyamide.
**) The footnotes in the table apply to the quantities

In experiments 7 to 23, the polymerization is carried out under reduced pressure by reducing the pressure from normal pressure to 4 ^r > 100 mm Hg within 30 minutes and at the same for 30 minutes

Who is being heard. The gel time is below flowing steam at 100 mm Hg.

example

The polymerization is carried out in the manner described in Example 1 using 500 g of the Salt of hexamethylenediamine with adipic acid, 500 g of distilled water and those mentioned in Table 9 Additives carried out, however, the temperature

door is increased to 275 ° C. The solution viscosity and the gel formation time at 290 ^° C. under flowing steam at normal pressure are measured for the polymers formed. The results are given in Table 9.

Table 9

No additives

Component (C)

Men- phosphorus compound men- alkali men

ge metal

link

Polymene Lo- GeI- station sensational bil- conditions viscous manic tiit Time. SId. Normal pressure 2.70 27 Normal pressure 2.72 50

1 not added

2 not added

not added - not -

added

Hypophosphorous 200 lithium 3 acid hydroxide

continuation Additives Men
ge 23 4 1 895 alkali
metal Men
ge S 22nd Lö- GcI- No. Component (C) link sensational
viscous bil-
dunijs- - Lithium- 3 Polymeri activity zcit,
Hours. 21 not added hydroxide station
conditions 2.72 49 3 0.45 Phosphorus compound Men
ge not - Phthalic anhydride added Normal pressure 2.70 48 4th 0.38 phosphorous acid 200 not _ 1,2-cyclohexane added diminished 2.70 45 5 dicarboxylic anhydride 0.38 not added - potassium 2 pressure 1,2-cyclohexane hydroxide diminished 2.71 120 6th dicarboxylic anhydride 0.38 not added _ potassium 2 pressure 1,2-cyclohexane hydroxide diminished 2.72 120 7th dicarboxylic anhydride 0.51 phenylphos- 200 Sodium- 2 pressure Phthalic acid phonic acid hydroxide diminished 2.72 124 8th 0.51 Phenylphosphorus 200 Potassium- 2 pressure Phthalic acid acid methoxide diminished 2.72 125 9 0.45 Sodium hypo- 200 not - pressure Phthalic anhydride phosphite added diminished 2.88 37 10 0.45 Potassium hydrogen 200 Nalxium 2 pressure Phthalic acid phosphite hydroxide diminished 2.70 53 11th phosphorous acid 200 pressure diminished phenylphos- 50 pressure phonic acid

The statements in Example 8 apply to the quantities in the table.

In experiments 4 to 11, the polymerization is carried out under reduced pressure as in Example 8, and the gelation time is under flowing Determined water vapor of 100 mm Hg.

Example 10

The polymerization is carried out in the manner described in Example 1 using 500 g of the Salt of m-xylylenediamine with adipic acid, 1000 g

distilled water and the additives listed in Table 10. The solution viscosity and the gel formation time at 270 ° C under flowing water vapor of normal pressure are for the Measured polymers formed. The results are given in Table 10.

The results show that in comparison to other polymers with the same solution viscosity the polymers containing a phosphorus compound, an alkali metal compound and o-phenylenediamine, the gelation can be suppressed to a remarkable extent.

Table 10

No. Additives Men-phosphorus compound
ge Men
ge alkali
metal Men
ge Polymeric Lo- GeI- V Component (C) link station
conditions sensational
viscous bil-
manic - not added _ not _ activity Time,
Hours. 1 not added added Normal pressure 2.23 18th - phenylphos- 200 not - 2 not added phonic acid added Normal pressure 2.25 16 phenylphos- 200 sodium 2 3 not added phonic acid hydroxide Normal pressure 2.23 38 - sodium 200 sodium 3 4th not added hypophosphite hydroxide Normal pressure 2.24 37 - * phenylphosphonic 200 sodium 2 5 not added acid hydroxide Normal pressure 2.23 38 phosphorous acid 200 sodium 3 6th not added hydroxide Normal pressure 2.23 38 0.45 not added - not - 7th o-phenylenediamine added diminished 2.24 37 pressure

Forlset / utm

No. Additives Men
ge Phosphorus compound Men
ge Alkali-
metal- Men- l'polymeri- Lo- GeI- Component (C) connection station
conditionscn sensational
viscous bil-
manic 0.39 not added not tiit Time,
Hours. 8th m-xylylenediamine added diminished 2.23 15th 0.32 not added - not - pressure 9 2-ethylhexylaniine added diminished 2.23 23 0.45 phenylphos- 200 sodium 2 pressure IO o-phenylenediamine phonic acid hydroxide diminished 2.23 82 0.51 phenylphos- 200 sodium 2 pressure Il 3-methyl-o-phenylene- phonic acid hydroxide diminished 2.25 85 diamine 0.32 phenylphos- 200 sodium 2 pressure 12th 2-ethylhexylamine phonic acid hydroxide diminished 2.22 43 0.45 phenylphos- 200 lithium 2 pressure 13th o-phenylenediamine phonic acid hydroxide diminished 2.24 79 0.45 hypophosphorous 200 sodium 3 pressure 14th o-phenylenediamine acid methoxide diminished 2.23 88 0.45 phosphorous acid 200 Sodium- 3 pressure 15th o-phenylenediamine methoxide diminished 2.23 85 2.00 Sodium hypo- 200 sodium 3 pressure 16 o-phenylenediamine phosphite hydroxide diminished 1.41 123 0.45 Sodium hypo- 200 sodium 8th pressure 17th o-phenylenediamine phosphite hydroxide diminished 1.55 50 0.45 Sodium hypo- 500 sodium 2 pressure 18th o-phenylenediamine phosphite hydroxide diminished 2.16 100 0.45 Sodium hypo- 30th Sodium- 2 pressure 19th o-phenylenediamine phospit hydroxide diminished 2.23 40 0.45 Sodium hypo- 200 not - pressure 20th o-phenylenediamine phosphite added diminished 2.27 35 0.45 Phenylphosphine 200 sodium 2 pressure 21 o-phenylenediamine acid hydroxide diminished 2.22 105 pressure

The statements in Hebeispiel apply to the quantities

In experiments 7 to 21, the polymerization is carried out under reduced pressure in the manner described in Example 8. The gel formation rate is determined under flowing hydrogen of 100 mm Hg.

Example Il

) l) 0g of the salt of hexamethylenediamine with adipic acid, 1.94 g of o-phenylenediamine, 0.30g of sodium hypophil monohydral. 0.22 g of sodium hydroxide and 500 g of distilled water are placed in an autoclave. The polymerization is carried out at 27TC under vermiiulerlem pressure comparison, a polymerization under normal pressure in the absence iles (ielbildiingsinhibilors performed /. The polymer from the first Versiah has a gelation / eil of hH hours at 27O ¹ C and a l.ösungsviskositäl 2 .bH. The polymer from the experiment has a (ielbildutigs / eit of Π hours at 270 ° C and a solution viscosity of 2.70.

The polymers are processed by melt spinning. The obtained ciarn is dyed with the Säuielarbsloff “Suminol level Ruhinol i (iP” (Color Index Acid Red 57). The Ciarn from the polymer according to the invention is ^r > 8 and for the yarn from the comparative polymer 3.2. The yarn from the polymer is brilliant.) The airing is thus dyed more richly and purely.

15 e i s ρ i e I 12

Poly-m-xylylene adipamide is prepared in the manner described in Example I, with al> (ielbildunginhibitor phthalic anhydride in an amount of 0.45%, based on polyamide, phenylpliosphonous acid in an amount of 200 ppm, calculated as phosphorus and based on on the weight of polyamide and sodium hydroxide are used in such an amount that the molar ratio of the total alkali metal to phosphorus is 2, compared with a polymerization without addition, de-(oil formation inhibitor. The two new polymers have a 1. Solution viscosity of 2.1 years

The polymers are processed by melt spinning under the following conditions: Spinning lemneratur 260 "C; Diisendiin.-Hmesser 0.3 mm; number of dei

25 26

Nozzle bores 20; Thru salt 12.3 g / minute; Must be deductible. In contrast, the polymer that the

speed 910 m / min. The product will contain gelation inhibitor, spin smooth and

stretching with a draw ratio of 3.1 at a speed, and after about 10 days of continuous

drawn at 640 m / minute, with a shiny, well-chem spinning hardly any yarn breaks at the nozzle.

Ij looking yarn of 40 d / 20 f is obtained. With 5 Likewise, there is no increase in the back pressure at the nozzle

Spinning the polymer which found no gel formation inhibitor. The number of knots per million meters of the

tor contains, occur after 2 days of uninterrupted drawn yarn from the polymer that the

Often yarn breaks appear at the nozzle. The gelation inhibitor it contains is much less than at

The back pressure at the nozzle increases so quickly that the nozzle

replaced and the spinning machine cleaned inside κι determined by the slot method.

Claims (7)

Patent claims: 1. Mixtures based on polyamides, phosphorus compounds and alkali metal compounds, containing a polyamide and A) at least one of the following phosphorus compounds: a) Phosphinic acid compounds of the formula
O Il R ₁ -P-OX ₁ 10 component (C) at least one cyclic dicarboxylic acid anhydride of the formula O = C C = O and / or its hydrolyzed product in an amount of 0.01 to 2% by weight, based on: Weight of the polyamide, where Y in the formula for a group of the formula b) Phosphonous acid compounds of the formula OX ₂ ^2Ü R ₃ -P-OX ₃ c) phosphonic acid compounds of the formula Il R ₄ -P-OX ₄ OX ₅ d) Phosphorous acid compounds of the formula OR ₆ J5 R ₅ OP-OR ₇ 40 B) at least one alkali metal compound formula Z-OR ₈ where the amount of component (A) is 50 to 1000 ppm (calculated as phosphorus), based on on the weight of the polyamide, and the amount of component (B) 1 to 5 mol (calculated as Alkali metal) per mole of component (A), and in the formulas R | until \ l? Are hydrogen, alkyl, aryl or cycloalkyl, Rs is hydrogen, alkyl, aryl or cycloalkyl, Xi to X5 are each hydrogen, alkyl, aryl, cycloalkyl or alkali metal, Z is an alkali metal and one of the radicals Ri to R? and one of the radicals Xi to X ', together form a ring. 2. Mixtures based on polyamide according to claim 1, characterized in that the amount of Component (A) 100 to 500 ppm, calculated as phosphorus and based on the weight of the Polyamide, and the amount of component (B) 2 to moles, calculated as alkali metal, per mole of μ Component (A) is. 3. Polyamide-based mixtures according to claim 1 and 2, characterized in that they are additionally used as where the radicals R are identical or different and are hydrogen, alkyl, substituted alkyl, aryl, cycloalkyl, halogen, nitro or hydroxyl, R is an alkylene radical and η is an integer from 1 to A. 4. Polyamide-based mixtures according to Claims I to 3, characterized in that the component (C) is present in an amount of from 0.1 to 1 percent by weight based on the weight of the polyamide. 5. Polyamide-based mixtures according to claim I to 4, characterized in that they are additionally used as Component (D) at least one o-phenylenediamine and / or its derivatives in an amount of 0.01 to 2% by weight, based on the weight of the polyamide. 6. Polyamide-based mixtures according to claim 5, characterized in that they are the component (C) contained in an amount of 0.1 to 1% by weight based on the weight of the polyamide. 7. A method of preventing a polyamide from gelling in a molten state, thereby marked that A) at least one of the following phosphorus compounds: a) Phosphinic acid compounds of the formula
O R ₁ -P-OX ₁ b) Phosphonous acid compounds of the formula OX ₂ R ₃ -P-OX ₃ and c) phosphonic acid compounds of the formula Il R ₄ -P-OX ₄
OX ₅ d) Phosphorous acid compounds of the formula OR ₆